This is the 35 USC national stage of International Application PCT/NL00/00434 filed on Jun. 22, 2000.
The present invention relates to a process for immobilizing arsenic ions comprising oxidizing arsenic to pentavalent arsenic and supplying trivalent iron, and subsequently immobilizing the pentavalent arsenic as an iron arsenate.
Arsenic is an important and unwanted by-product in many metallurgical processes. For example, copper ores contain a substantial amount of arsenic, which is undesired for health and environmental reasons and must therefore be separated from the copper metal and be safely disposed of In pyrometallurgic processes, arsenic is usually separated from off-gas and converted to arsenic trioxide (As2O3). This trivalent arsenic compound is unstable, since arsenic is slowly oxidised to pentavalent arsenic. Where there is no use for such arsenic trioxide, it should be carefully deposited so as to avoid leaching of arsenic to the aquatic environment.
A conventional method for separating and disposing arsenic form metallurgical process streams involves chemical oxidation of the arsenic-containing liquid, which also contains iron, in an oxygenated autoclave at about 90xc2x0 C. at pH 3-4. The pentavalent arsenic thus produced is then converted to a stable insoluble ferric arsenate typically having a molar Fe/As ratio of at least 4 (see e.g. G. B. Harris, xe2x80x9cThe Control and Disposal of Arsenic in Hydrometallurgical Systemsxe2x80x9d, 24th Annual CIM Hydro-metallurgical Conference, Toronto, Ontario, Aug. 20-21, 1994). This chemical oxidation using autoclaves is expensive because of the use of expensive equipment and chemicals, and because of high training costs to avoid personal hazard.
U.S. Pat. No. 4,888,293 discloses a process wherein a mixture of pyrite and arsenopyrite with a molar Fe/As ratio of about 4:1 is treated with a mixed culture of Thiobacillus ferrooxidans, T thiooxidans and Leptospirillum ferrooxidans resulting in a strongly acidic (pH 1.1) solution. This solution is neutralised and produces a precipitate containing iron arsenate and jarosite, having an Fe/As ratio in the order of 8.
A new process for the immobilisation of arsenic has been found, involving biological oxidation of arsenic to pentavalent arsenic as well as supply of trivalent iron, in particular by biological oxidation of scrap iron. This oxidation results in effective oxidative solubilisation of the metals followed by effective disposal of the arsenic. The process is defined in the appending claims.
The oxidation of trivalent arsenic in the presence of iron is carried out using suitable oxidizing bacteria. In general, these bacteria assist in the oxidation of divalent iron to trivalent iron using oxygen and acid (protons). Suitable bacteria are usually present in the raw materials (ores) from which the arsenic waste originates. Suitable bacteria can also be derived form other biological, aerobic waste treatment plants. The bacteria capable of oxidizing iron and arsenic will normally spontaneously become dominant as a result of the process conditions which can be selected by the skilled person. The bacteria can be heterotrophic such as soil bacteria of the genera Pseudomonas, Achromobacter, Bacillus (especially B. cereus) and Alcaligenes (especially A. faecalis). It is preferred, however, that the bacteria are autotrophic bacteria, as these do not need other carbon sources than carbon dioxide, which may be present in sufficient amounts in the waste to be treated, e.g. in the form of carbonates (FeCO3) or with the air supplied to the oxidation process. Suitable autotrophic bacteria for oxidizing sulphur and/or iron species include mesophilic bacteria, in particular Thiobacillus species such as T. ferrooxidans and T. thiooxidans and Leptospirillum species including L. ferrooxidans, moderately thermophilic bacteria, in particular Acidomicrobium, Sulfobacillus and Thiobacillus species and extremely thermophilic bacteria, in particular Sulpholobus and Acidiamus species such as S. acidocaldarius. Mesophiles are typically active at temperatures from about 20xc2x0 C. to about 45xc2x0 C., moderate thermophiles at about 45 to 65xc2x0 C. and extreme thermophiles at between about 65 and 90xc2x0 C.
The biological oxidation is carried out at a pH between 0.5 and 4, especially between 1 and 3, at a temperature (depending on the type of bacteria used) between ambient temperature and about 85xc2x0 C. or even up to 90xc2x0 C. A process using mesophilic bacteria is preferably operated at 30 to 45xc2x0 C., while a process using thermophilic bacteria is preferably performed at 50 to 80xc2x0 C. Hyperthermophilic bacteria capable of activity between about 75 and 90xc2x0 C., which can be isolated from hot pools and other hot water sources, can be used according to the invention at those high temperatures. The biological oxidation of arsenic usually requires the presence of a mineral catalyst, in particular a (semi-)noble metal or a metal or metal complex in the galvanic series from noble metals downwards to complexes comparable to pyrite-type minerals. The latter include pyrite, chalcopyrite and molybdenite. The catalyst should have a clean surface.
The reaction for oxidative arsenic trioxide dissolution by ferric ion can be represented by the following equation:
As2O3+2Fe2(SO4)3+5 H2Oxe2x86x922H3AsO4+4FeSO4+2H2SO4
The ferric ion is regenerated by the bacteria using oxygen, so that the net reaction is conversion of As2O3 with oxygen and water to H3AsO4.
The trivalent iron necessary for producing the insoluble arsenic compound can be added as such, if an economic source of soluble trivalent iron is available. However, a suitable source of readily soluble trivalent iron is often not available, while a cheap source of iron may be present, especially at a mining site. A common source of iron is pyrite (FeS2) or pyrrhotite (FeS or Fe7S8). Also oxidation products thereof, such as iron oxides, can be used. Most advantageously, the source of iron is iron scrap, which is usually available at mining sites and other sites where arsenic should be disposed, e.g. in the form of broken or unused equipment, rails, scaffolding or the like.
It is preferred then that the trivalent iron is produced by biological oxidative dissolution of the iron source, using the same bacteria as those assisting in the oxidation of arsenic. The oxidations can be performed simultaneously in the same reactor, but preferably, the generation of trivalent iron in solution is performed in a separate reactor. In the former case, pyrite used for catalysing the arsenic oxidation can be used to provide iron for ferric arsenate precipitation as well.
The precipitation of arsenic in a stable form occurs with an excess of ferric ion resulting in a stable amorphous ferric arsenate. The stability was found to be satisfactory when the Fe/As molar ratio in the precipitate is greater than 4. For a 10 g/l arsenic solution, the precipitation starts at about pH=3. The following reaction may occur:
2H3AsO4+4Fe2(SO4)3+22H2Oxe2x86x922FeAsO4.3Fe(OH)3.2H2O+12H2SO4
The overall reaction produces acid. However, the iron source may contain some acid-consuming gangue. Furthermore, the acid production can be reduced by using iron-bearing minerals with lower sulphur levels. When pyrrhotite is used instead of pyrite, the bio-oxidation of the iron-bearing mineral becomes acid-consuming rather than acid-producing.
A preferred option according to the invention is to precipitate the arsenic acid under carefully controlled conditions as crystalline scorodite (FeAsO4.2H2O; Fe/As=1), which considerably reduces the iron requirement and hence the acid production. This requires a molar ratio of iron to arsenic of about 1:1. Thus, the amount of iron added is adjusted such that this ratio is achieved in the precipitation reactor. Preferably between 0.9 and 1.8 mole of iron is used per mole of arsenic present in the arsenic-containing waste to be treated. The net reaction is than as follows:
xe2x80x832H3AsO4+Fe2(SO4)3+2H2)xe2x86x922FeAsO4.2H2O+3H2SO4
When the iron dissolution is assumed to be the rate-limiting step, the kinetics of the overall process rises considerably when less iron is needed. The oxygen requirement will then go down, bringing down both the operational cost and the capital cost.
The precipitation of crystalline scorodite is favoured, although not necessary. It can take place at elevated temperatures (above 80xc2x0 C.) and at controlled pH (about 2-3, depending on concentrations). As thermophiles can be used for oxidizing both the iron and the arsenic, the invention is also suitable for high-temperature applications.